A nanoporous metal-organic framework as a renewable size-selective hydrogen-bonding catalyst in water

Article abstract of DOI:10.1039/c9dt01763a

A novel squaramide-containing metal-organic framework (MOF) material has been designed and synthesized. A detailed X-ray crystal structure analysis showed that four squaramides of this MOF adopted two orientations in each dependent nanopore, confirming th

Full text of DOI:10.1039/c9dt01763a

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ISSN 0306-0012
COMMUNICATION
Douglas W. Stephen et al.
N-Heterocyclic carbene stabilized parent sulfenyl, selenenyl,
and tellurenyl cations (XH , X = S, Se, Te)
+
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DOI: 10.1039/C9DT01763A
ARTICLE
Nanoporous Metal–organic Framework as Renewable Size-
selective Hydrogen-Bonding Catalyst in Water
Received 00th January 20xx,
Accepted 00th January 20xx
a
a
a
b
a
a
a
Yanhong Liu, † Ju Ma, † Pengyan Wu,* Jia-Jia Zheng, Xueqin Tian, Min Jiang, Yumei He, Han
a
a
Dong and Jian Wang*
DOI: 10.1039/x0xx00000x
A novel squaramide-containing metal–organic framework (MOF) material has been designed and synthesized. Detailed X-
ray crystal structure analysis showed that four squaramides of this MOF adopted two orientations in each dependent
nanopore, confirming that two carbonyl and two N-H groups pointed simultaneously to the inside of the one-dimensional
nanometer channel. The MOF was applied as an efficient bifunctional hydrogen-bonding catalyst for Michael additions of
1
,3-dicarbonyl compounds to nitroalkenes in pure water, boosting the catalytic efficiency by up to approximately five
times the value afforded by the homogeneous control, as well as exhibiting a highly size-selective catalytic performance
and good renewability. The catalytic mechanism was also discussed in detail. The present study provides a highly
promising approach to achieving dual-activation catalytic centers in a single system, which function as microscopic
chemical reactors that allow interaction and fast transport of substrate molecules in their cavities.
Squaramide derivatives are powerful hydrogen-bonding
organocatalysts for key bond-forming transformations among many
eligible HB catalysts reported to mimic biological machinery.
Introduction
1
6,17
Inspired by their natural ability, synthetic chemists have long sought
to mimic the properties of biological systems using abiotic
This is not only owing to squaramides derived from squaric acid
possessing hydrogen-bond accepting and donating functionalities
through their carbonyl and N–H groups, respectively, but also
because of their improved acidity originating from the potential for
resonance stabilization of enhanced electron density of the partially
1
platforms. This is due to their potential for developing synthetically
useful catalysts that match or even exceed the capabilities of
natural systems. Considering the pivotal role of H-bonding in
myriad natural processes, hydrogen-bond (HB) organocatalysis has
emerged as a biomimetic alternative to enzyme catalysis, which can
activate electrophilic moieties toward nucleophilic addition via
2
1
8
aromatic squaramide ring. However, their strong hydrogen-
bonding ability also drives self-aggregation and salvation to form
dimers or oligomers, causing deactivation during the homogeneous
3
,4
cooperative hydrogen bonding.
MOFs) or porous coordination polymers (PCPs) are crystalline
materials with extended structures that can be utilized in many
Metal–organic frameworks
1
9
catalysis and resulting in serious recycling issues.
(
Based on the above MOF characteristics, incorporating
squaramide derivatives as pillaring struts into MOFs would prevent
5
,6
7,8
9
fields, such as gas sorption, sensing and optical, drug delivery,
1
0–12
and catalysis.
heterogeneous catalysts because of their tunability, permanent However, squaramide-containing MOFs are rare; e.g., Hupp,
In recent years, MOFs were studied as novel detrimental self-association due to their ordered structure.
2
0
1
3
microporosity, and defined reaction environments. Moreover, the Farha, and Mirkin et al. first demonstrated the functionalization of a
extensive distribution of active sites and confined inner spaces in heterogeneous framework with an acidic squaramide derivative for
MOFs make them excellent enzyme-like catalysts possessing the the biorelevant Friedel–Crafts reaction between β-nitrostyrene and
integrated advantages of heterogeneous and homogeneous indole; Cohen et al. used a new squaramide-based ligand to
catalysis, such as size-selectivity, easy separation and recycling, and construct MOFs as active catalysts for the Friedel–Crafts reaction;
1
4,15
high activity.
Despite these advances, the rational design of our group has also constructed a novel squaramide-containing MOF
efficient enzyme-like MOF catalysts remains difficult.
for the luminescence-selective detection of lactose in aqueous
solution and in milk. To the best of our knowledge, there are no
reports of squaramide-containing MOFs as bifunctional hydrogen-
bonding donor-acceptor catalysts for one reaction, because it is
very difficult to control the distribution and configuration of
squaramide moieties inside the pore cavities of the designed MOFs.
Herein, we report the synthesis of a new squaramide-containing
MOF, which is formed by using 3,3'-((3,4-dioxocyclobut-1-ene-1,2-
a. School of Chemistry and Materials Science & Jiangsu Key Laboratory of Green
Synthetic Chemistry for Functional Materials, Jiangsu Normal University, Xuzhou,
2
21116, P. R. China. E-mail: wpyan@jsnu.edu.cn; wjian@jsnu.edu.cn
b.
Institute for Integrated Cell-Material Sciences (WPI-iCeMS), Kyoto University,
Ushinomiya cho, Yoshida, Sakyo-ku, Nishikyo-ku, Kyoto 606-8501, Japan.
These authors contributed equally to this work.
†
diyl)bis(azanediyl))dibenzoic acid and Zn(NO
3
)
2
·6H
2
O
under
Electronic Supplementary Information (ESI) available: Additional experimental
details, crystal data and related spectra. See DOI: 10.1039/x0xx00000x
solvothermal conditions. We envisioned that the well-positioned
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squaramide group orientation and the catalytic sites within the atoms of two different carboxylate ligands andVietwwAorticleotOhnelinres
large pores of this MOF would combine HB accepting and donating belonging to hydroxyl groups; the other cryDstOaIl:lo10g.r1a0p3h9/icC9zDinTc01a7t6o3mA
bifunctionality to activate the catalytic substrates. This MOF shows is octahedrally coordinated to four oxygen atoms belonging to the
good catalytic activity toward Michael addition of nitroalkenes and carboxylate groups of four dbda2 ligands and two oxygen atoms
−
1
,3-dicarbonyl compounds in the heterogeneous state and displays
belonging to hydroxyl groups (Figure 1a and Figure S1 in the SI).
The Zn–O bond distances are 1.91(0)–2.12(7) Å. The infinite zinc
oxyhydroxide chain can be regarded as a secondary building unit
size-selective catalytic behavior for a large substrate scope in water.
(
SBU). These chains, which are parallel to the a-axis, are further
interconnected through the dbda2 moieties to generate a three-
−
2
−
dimensional architecture. It is noteworthy that the dbda ligands in
Zn–DBDA all showed a μ -η :η :η :η coordination mode (Figure S2
4
1
1
1
1
in the SI). A one-dimensional nanometer channel with a cross-
2
section of 21.7 × 14.5 Å (based on the van der Waals radii of the
atoms) was viewed along the [100] direction (Figure 1c). In each
dependent channel, two N–H and two carbonyl moieties from four
different squaramide-based ligands point to the inside of the pore
cavity (Figure 1b), facilitating interaction and activation of the
hydroxyl or related moieties in the substrates. The solvent-
3
accessible volume was calculated as 1,865.8 Å using the PLATON
program, which is 55.0% of the unit-cell volume. The Brunauer–
Emmett–Teller surface area calculated from CO sorption data for
2
Zn–DBDA was 342 m2 g−1 (Figure S3 in the SI). The
thermogravimetric analysis (TGA) curve of Zn–DBDA showed that its
structure could be maintained up to 430°C, with a weight loss of
4
3.7% between 26°C and 430°C corresponding to the loss of five
DMF molecules (calculated as 44.04%) (Figure S4 in the SI);
additionally, TGA clearly indicated that the guest molecules were
completely excluded after Zn–DBDA was dried at 120°C under
vacuum. Interestingly, the index of powder XRD patterns of the Zn–
DBDA bulk sample immersed in water for 7 days evidenced
maintenance of the framework, indicating the feasibility of Zn–
DBDA as a sensing or catalytic material in aqueous solution (Figure
S5 in the SI).
Table 1. Optimization and control experiments of Michael addition of Hacac with β-
Figure 1. (a) Construction of Zn–DBDA consolidated by squaramide-based ligands and
coordinated environment of Zn2+ ions in Zn–DBDA. (b) Two N–H moieties and two
nitrostyrene.a)
O
O
carbonyl moieties from four different squaramide-based ligands as potential
catalytically active sites pointing to the inside of the nanometer 1D channel. (c)
Connolly surface (radius: 1.4 Å) of Zn–DBDA along the [100] direction. Gray represents
the outer surfaces of the channels, while yellow represents their inner surfaces. For
clarity, the hydrogen atoms are omitted in (b).
NO2
O
O
Catalyst
+
NO2
H2O, rt, 6hrs
Entry
Catalyst
Zn(NO
dbda
Solvent Yieldsb)
1
2
3
4
5
3
)
2
H
H
2
O
O
n.d.
19
20
n.d.
>99
H
2
2
Results and discussion
Crystallographic description of Zn–DBDA
Zn(NO ) /H dbda
H O
3
2
2
2
---
H
H
2
O
O
Zn–DBDA
2
The solvothermal reaction of Zn(NO
dioxocyclobut-1-ene-1,2-diyl)bis(azanediyl))dibenzoic acid (H
in N,N-dimethylformamide (DMF)/ethanol gave the pale-yellow
block crystal Zn–DBDA {Zn1.5(OH)(dbda)ˑ5DMF} in high yield (85%).
3
2
) ·6H
2
O
and 3,3'-((3,4-
a)
Reaction conditions: Zn–DBDA (5.0 μmol of squaramide based on TGA), β-
nitrostyrene (0.1 mmol), Hacac (0.2 mmol), 3.0 mL of water, reaction time: 6 h;
Determined by H NMR.
2
dbda)
b)
1
n
Zn–DBDA was determined by single-crystal X-ray diffraction to Catalytic experiments on Michael addition
crystallize in the monoclinic space group P2(1)/c and was found to
Our catalytic experiments were focused on Michael addition of
be
a
three-dimensional framework containing infinite one- nitroolefins and dicarbonyl compounds.21 The catalytic activity of
chains connected through the dbda2
(OH)
−
dimensional [Zn
ligands. In an asymmetric unit of the [Zn
atoms adopt tetrahedral coordination geometry with two oxygen where the reaction was conducted in a flask with 0.1 mmol of β-
3
O
8
(OH)
2
]
n
activated Zn–DBDA as a catalyst was assessed for Michael addition
3
O
8
2
]
n
chains, two zinc of acetylacetone (Hacac) with β-nitrostyrene as a model reaction,
2
| J. Name., 2012, 00, 1-3
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nitrostyrene, 0.2 mmol of Hacac, and 0.5 mol% of Zn–DBDA as a
catalyst in 3 mL of H
With these optimal reaction conditions in handV,iewwAerticfleuOrtnhliener
O at room temperature, giving a yield of >99%, surveyed the generality and scope of the prDeOseI:n1t0p.1r0o3t9o/cCo9lDaTc0r1o7s6s3Aa
2
which shows that Zn–DBDA is an effective catalyst for Michael range of β-nitroolefins with Hacac in the presence of 0.5 mol% of
addition of β-nitrostyrene and Hacac. Simultaneously, a series of Zn–DBDA. As summarized in Table 2, the reactions of all β-
controlled experiments were investigated under the same nitroolefins having electron-donating substituents such as methyl
conditions to eliminate the factors affecting catalytic performance and methoxy or electron-withdrawing substituents such as bromine
and unveil the catalytic nature of Zn–DBDA. A reaction conducted in at the ortho- and meta-positions, and nitro, with Hacac gave the
the absence of Zn–DBDA yielded no detectable conversion. The use corresponding Michael adducts in high yield (reaching 85%). When
of the ligand H
a yield of only 19% (Table 1, entries 4 and 2), while Zn(NO
displayed no catalytic activity under the same conditions; even a yield, with only 25% product conversion (Table 2, Entry 7). It is
simple mixture of Zn(NO and H dbda afforded only similar speculated that the large β-nitroolefins have limited access to
2
dbda itself rather than Zn–DBDA as the catalyst gave the reactant was the bulky nitrostyrene, (E)-1-(tert-butoxy)-4-(2-
3 2
)
nitrovinyl)benzene, the reaction gave a dramatically decreased
3
)
2
2
conversion to that of the ligand itself (Table 1, entries 1 and 3). catalytic sites inside the MOF tunnel, preventing easy attainment of
These results revealed that this squaramide-containing MOF Zn– suitable transition-state geometry, thus exerting size-selective
DBDA can serve as an excellent catalyst for the Michael addition catalysis.
reaction, facilitating close proximity between squaramide groups
governing catalytic functional groups and the substrates within
confined spaces.
Table 3. Evaluation of Zn–DBDA in catalytic Michael addition reactions of various 1,3-
dicarbonyl compounds with β-nitrostyrene.a)
O
O
NO2
O
O
Catalyst
Table 2. Evaluation of Zn–DBDA in catalytic Michael addition reactions of various β-
nitroolefins with Hacac.a)
R1
R2
+
NO2
R1
R2
H2O, rt, 6hrs
O
O
Yieldsb)
O
O
Catalyst
Entry
1
1,3-dicarbonyls
Molecular Size
NO2
+
R
NO2
H O, rt, 6hrs
R
2
O
O
Yieldsb)
>99
Entry
1
β-nitrostyrenes
NO2
Molecular Size
>99
O
O
2
3
95
90
O
NO2
2
3
95
91
O
O
O
O
O
NO2
O
O
4
5
33
3
Br
NO2
4
93
91
O
O
Ph
NO2
5
6
O
O
Br
6
n.d.
Ph
Ph
NO2
NO2
a)
Reaction conditions: Zn–DBDA (5.0 μmol of squaramide based on TGA), β-
nitrostyrene (0.1 mmol), 1,3-dicarbonyl compounds (0.2 mmol), 3.0 mL of water,
reaction time: 6 h; Determined by H NMR.
86
25
O2N
b)
1
Encouraged by these results, the substrate scope of the reaction
was also investigated with several 1,3-dicarbonyl compounds as
nucleophiles. As shown in Table 3, more than 90% of Michael
products were detected when methyl 3-oxobutanoate and ethyl 3-
oxobutanoate were used (Table 3, entries 2 and 3). Conversely, as
the molecular sizes of the 1,3-dicarbonyl substrates increased, a
7
O
a)
Reaction conditions: Zn–DBDA (5.0 μmol of squaramide based on TGA), β-
nitroolefins (0.1 mmol), Hacac (0.2 mmol), 3.0 mL of water, reaction time: 6 h;
b)
1
Determined by H NMR.
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significant decrease in the yield of Michael products was observed, solid was then washed several times with water/ethaVnioewl tAorticrleemOnolivnee
as shown by the 33% formation of tert-butyl 2-acetyl-4-nitro-3- residual substrate from the surface. The IRDsOpIe: 1c0tr.1u0m39/oCf9ZDnT–0D17B6D3AA
phenylbutanoate (Table 3, entry 4). The presence of 1- with absorbed β-nitrostyrene was compared to that of Zn–DBDA. A
phenylbutane-1,3-dione resulted in only a trace yield (about 3%) red shift occurred for the splitting of the peak at 1314 cm−1
under the same experimental conditions (Table 3, entry 5). A belonging to the N=O stretching vibration, comparable with the
bulkier substrate, 1,3-diphenylpropane-1,3-dione, was employed, corresponding peak in the spectrum of free β-nitrostyrene (1343
−
1
resulting in inefficient Michael addition with an undetectable yield cm ) (Figure S8 in the SI). Additionally, the emerging peak at 1605
Table 3, entry 6). This size-selective catalysis with comparable cm− for the Hacac-impregnated Zn–DBDA is attributed to the
1
(
reactivity provides further evidence that the catalytic reactions characteristic C=O stretching vibration peak and shows a red shift
might occur in the channels of Zn–DBDA and that the two from 1629 cm− (for free Hacac) (Figure 2b and Figure S9 in the SI).
substrates might be simultaneously activated in the same channel. This suggested that the adsorption of β-nitrostyrene and Hacac
All the results demonstrated that Zn–DBDA was an efficient size- occurred within the MOF channels via weak interactions. Moreover,
1
selective catalyst toward Michael addition reactions.
Catalytic mechanism discussion
1H NMR analysis of the Zn–DBDA solid after immersion in a H
solution containing β-nitrostyrene and Hacac also demonstrated
2
O
To further verify and understand the catalysis, a luminescence that Zn–DBDA could adsorb one molecular stoichiometric amount
titration between Zn–DBDA and β-nitrostyrene or Hacac was of β-nitrostyrene and Hacac per pore (Figure 2c and Figures S10 and
further applied to investigate the interaction between the catalyst S11 in the SI). Extensive molecular force field-based calculations
and substrates. Upon excitation at 320 nm, Zn–DBDA showed an were further performed to gain insight into the interaction between
intense luminescence band at about 470 nm, derived from ligand- Zn–DBDA and β-nitrostyrene/Hacac by using a universal force field
based emission. Adding 0.23 mM β-nitrostyrene to 0.55 mM Zn– as implemented in the Gaussian 09 program. As shown in Scheme
DBDA suspension led to approximately 71% quenching of the 1(A), close contacts were observed between the oxygen atoms of
emission intensity of the Zn–DBDA, with a Stern–Volmer constant the carbonyl groups of squaramide moieties from Zn–DBDA and the
3
−1
(KSV) calculated as 9.24 ± 0.12 × 10 M (Figure 2a and Figure S6 in hydrogen atoms from isomerized Hacac. Meanwhile, close contacts
the SI). It is noteworthy that fluorescence titration upon adding were also observed between the oxygen atoms of β-nitrostyrene
Hacac also revealed 65% quenching of the Zn–DBDA emission with and the N-H groups of squaramide moieties from Zn–DBDA, and the
3
−1
a KSV of 2.37 ± 0.1 × 10 M (Figure S7 in the SI). The results nearest O···H distances were only 2.38 and 2.16 Å, respectively,
indicated that both Hacac and β-nitrostyrene can interact with Zn– which are typical for hydrogen bonds; this result is also consistent
DBDA.
with the experimental results. All the results indicated that both
Hacac and β-nitrostyrene can be adsorbed in the channel of Zn–
DBDA and further activated by the squaramide groups.
Scheme 1. Representation of the interaction between Zn–DBDA and β-
nitrostyrene/Hacac computed by molecular force field-based calculations (A). Proposed
mechanism of Michael addition catalyzed by Zn–DBDA (B and C).
Figure 2. (a) Family of fluorescence spectra of Zn–DBDA (0.55 mM) upon adding β-
nitrostyrene up to 0.23 mM. (b) FT-IR spectra of Zn–DBDA (top), Zn–DBDA obtained
1
after absorption of Hacac (middle), and Hacac (bottom). (c) The H-NMR spectra after
nitrostyrene and Hacac adsorption in the Zn–DBDA.
Based on the above analysis and literature reports,22 we propose
a plausible dual-activation model for this Michael addition. As
shown in Scheme 1, firstly, catalyst Zn–DBDA simultaneously
activates nitroolefins and Hacac through hydrogen-bonding
Additionally, the desolvated Zn–DBDA was dispersed in a H
solution containing β-nitrostyrene or Hacac for one day. The filtered
2
O
4
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interactions to form intermediate A. Then, nucleophilic attack (B)
from the enolate to nitroolefins generates a new intermediate (C).23
Conclusions
View Article Online
DOI: 10.1039/C9DT01763A
In summary, a novel Zn(II)-based nanoporous MOF was
synthesized by incorporating the squaramide moiety as the
backbone, in which HB acceptor and donor sites existed
simultaneously in each dependent pore cavity. The well-
positioned squaramide group orientation and well-defined
pores of the frameworks made this MOF an efficient
bifunctional HB donor-acceptor catalyst for Michael addition
of 1,3-dicarbonyl compounds to nitroolefins in water with
good size-selectivity. The MOF was recycled by simple
Finally, the nitronate takes the proton from the catalyst to provide
the product along with regeneration of the Zn–DBDA catalyst.
Reproducibility
An essential feature of any catalyst from the viewpoint of
industrial application is its reusability over multiple reaction cycles.
We first demonstrated the heterogeneity of our catalytic system,
and gravity filtration was performed to remove the catalyst after
reacting for 2 h; the results demonstrated that the reaction was
nearly terminated within the next 4 h (Figure S12 in the SI). Besides, filtration and reused several times without significant loss of
at the end of the reaction, inductively coupled plasma (ICP) analysis activity. This study provides a highly promising approach to
of the reaction mixture filtrate revealed no Zn leaching, indicating achieving size-selective conversion by constructing dual-
that the catalytic reaction is indeed heterogeneous. Therefore, we activation catalytic centers in a single system, which function
investigated the catalytic activity and stability of Zn–DBDA samples as microscopic chemical reactors that allow interaction and
fast transport of substrate molecules in their cavities.
isolated via filtration from the catalytic reaction. Prior to each
catalytic run, Zn–DBDA was recovered and washed several times
with water, then used again for catalytic Michael addition in a fresh
solution. Hardly any loss of catalytic activity was observed; even
when undergoing catalytic recycling five successive times, the yield
of 3-(2-nitro-1-phenylethyl)pentane-2,4-dione remained nearly
constant at 98% for the 2nd, 98% for the 3rd, 96% for the 4th, and
Conflicts of interest
There are no conflicts to declare.
Acknowledgments
9
7% for the 5th run (Figure S13 in the SI). Furthermore, the powder
X-ray diffraction patterns for the five cycles showed that the We gratefully acknowledge financial support from the Natural
Science Foundation of Jiangsu Province for Outstanding Youth
No. BK20180105), the National Natural Science Foundation of
China (Nos. 21401087 and 21401086), Postgraduate Research
Practice Innovation Program of Jiangsu Province (No.
KYCX18_2103), PAPD and TAPP of Jiangsu Higher Education
Institutions.
crystalline phase of Zn–DBDA remained unaltered, indicating that
the catalyst structure was relatively stable during the reaction
(
(Figure S5 in the SI). Such remarkably high recyclability, high
&
efficiency, and size selectivity to substrates in catalytic Michael
addition make this approach suitable not only for laboratory-scale
research but also for industrial application.
Notes and references
Experimental
‡
Crystal data of Zn−DBDA: C33
45 7
H N O12Zn1.5, Mr = 829.8,
Synthesis of Zn–DBDA: A mixture of H
Zn(NO ·6H O (30 mg, 20 mM) was dissolved in DMF/ethanol (4/1, = 19.068(4) Å, α = 90.00, β = 90.09, γ = 90.00, V = 3393.0(12) Å ,
mL) in a screw-capped vial. The resulting mixture was placed in an
2
dbda (8.8 mg, 5 mM) and
Monoclinic, space group P2(1)/c, a = 5.9994(12), b = 29.661(6), c
3
3
)
2
2
-3
-1
Z = 4, Dc = 1.624 g cm , μ(Mo-Kα) = 1.146 mm , T = 296(2) K.
5
1
0
1
1
9212 unique reflections [Rint = 0.1398 ]. Final R
1
[with I > 2σ(I )] =
oven at 80°C for 1 day. After cooling, pale-yellow block crystals
were collected by filtration. Yield: 85%. Anal. calc. for
.0637, wR
2
(all data) = 0.1262, GOOF = 1.003. CCDC number:
810642.
C
3
24
H
22
N
4
O
9
Zn1.5: C 47.37%, H 3.64%, N 9.2%; Found: C 47.21%, H
D. J. Cram, Angew. Chem., Int. Ed., 1988, 27, 1009; J.-M.
Lehn, Angew. Chem., Int. Ed., 1988, 27, 89; B. H. Northrop, Y.
R. Zheng, K. W. Chi and P. J. Stang, Acc. Chem. Res., 2009, 42,
.67%, N 9.32%.
General Procedure for Catalysis Experiments: The catalyst Zn–
1
554; M. Yoshizawa, M. Tamura and M. Fujita, Science, 2006,
12, 251.
DBDA (0.01 mmol, based on Zn), nitroalkenes (1.0 mmol), Hacac
2.0 mmol), and 3.0 mL water were added sequentially to a 10 mL
3
(
2
3
4
Y. Inokuma, M. Kawano and M. Fujita, Nature Chem., 2011,
3
2
, 349; M. S. Rosen, C. L. Stern and C. A. Mirkin, Chem. Sci.,
013, 4, 4193.
round-bottom flask. The mixture was allowed to react at 25°C for 6
h. During this time, the reaction was monitored constantly by TLC.
After completion of the reaction, the heterogeneous catalyst was
filtered through filter paper for the recycling experiment. The
P. R. Schreiner, Chem. Soc. Rev., 2003, 32, 289; H. Xu, S. J.
Zuend, M. P. Woll, Y. Tao and E. N. Jacobsen, Science, 2010,
327, 986.
X. Fang and C.-J. Wang, Chem. Commun., 2015, 51, 1185; E.
T. Hennessy and E. N. Jacobsen, Nature Chem., 2016, 8, 741;
V. J. Lillo, J. Mansilla and J. M. Saá, Angew. Chem., Int. Ed.,
2016, 55, 4312; P. R. Schreiner and A. Wittkopp, Org. Lett.,
aqueous solution was extracted with Et
combined Et O was washed twice with water and dehydrated with
Na SO . After evaporation of Et O, the residue was purified by silica
2
O (3 × 3.0 mL). The
2
2
4
2
2
002, 4, 217.
gel flash column chromatography to afford the desired product. The
conversion was calculated from the H NMR data.
5
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